Production of chloroanthraquinoneacridone



Patented Mar. 1; 1932 V STTES INC., on NEW YORK, n. A CORPORATION orennnswnnn rn-onuo'rron or cnrononn'rnnsaumonnncrunonn e warren Jensen, on ivrnnnnnnvr, GERMANY, Assisnon 'ro GENERAL-nmmeweaxs,

rammin Applicationfiled January 1a, 1930, seritrna 42112.7, statesman J'aii u ary 5;;19'2' The present invention relates to the pro-r agents supplying halogen, such as sulphuryl I is chloride, toact on l-anilido-2-methylanthraquinone or on l-ortho-toluidoanthraquinoner' By the treatment of the said initial materials with chlorine or agents supplying chlorine, 1n trichlorbenzene or another su table organic l5 solvent as for'enample another halogen de-' concentration and the like, uniform compounds are not obtained, but mixtures of dif- V V thraqiuinoneacridone having the samedye ng 2O ferent products are formed, a

I have new observedthat by theaction of a chlorinating agent which term comprises chlorine and agents supplying chlorine, on

V l-anilido-2-methylanthraquinone or l-orthotoluidoanthraquin'one in trichlorbenzene and like solvents described in the patent already referred to, generally speaking chlorinated I anthraquinoneacridones are not directly 7 formed, but a mixture of different intermediate products, the latter v being then convertecl into 'chloroanthraquinoneacridones by the splitting ofi ofchlorine inythebform of hydrogen chloride. p .v

I have now foundtha'tthe aforesaid intermediate products are of diflerent'solubility in organic solvents and that the-intermediate product which is comparatively read-'1 I v p e of 'trichlor-benzene, The reaction mixture is V 1 "allowed to'zcool and is filtered by suction from the? crystalline precipitate. Tl'1e, filtrate is i' allowed to stand for oneonin'ore days; during ily soluble yields by the splittingofi of chlorine in the form of hydrogen chloride a sub- 40 stantially uniform anthraquinoneacridone containing about 5 atoms of chlorine. The

splitting off of chlorine in the form of hy- 'drogen chloride can be promoted by heating or by theadditionot reducing agents. Due V to, its greatersolubility the intermediateproduct yielding the said chloranthraqui noneacridone predominates-in the mother liquors obtained during the'chlorination and can be recovered therefrom by the, usual methods.- Frequently, however, it isalso contained in the product-which separates out, Y andin this'case it can be extracted therefroin for example by means. of suitable solvents.

[In order to obtain aslarge anamountf as possible .otthe new and valuable dyestufi' 017 I oi the intermediateproduct which yields the v same it is p'referabletocar'ry out the chlorin-- ationwhile excluding 'moisture, and; when employing gaseous chlorinating agentsfto; v carry out-the reaction as rapidly asp'ossible which maybe effected for example by using The substantially uniform 'anthraquinone a large'number of inletnozzles for the gas.

acridone containing about 5 atoms'ofichlo rine obtained according to my invention rivative of benzene, even while maintainlng "y1eldsfo'n boil ng "Wltlfl d ethylanlhnean an constant conditions such as temperature,"

thraquinoneacridone containing-about 4 atoms of'chlorlne, dyeing cotton orange. shades, and" furnlsh'lng on chlorinatlon a chloroan .anthraquinoneacridone series.-

v T he following examples Willi further'illus tratehoyvthe said inventionrn'aybecarried out in practic'e'but the invention is notre stricted to theseexamples; --The parts are by About l10 artsofchlorine areledat from a-n ilido-2-methylanthraquinone in i 350 parts this time microscopic needles separate; whichdissolve inconcentratedsulphuric-acid givinq an orangexred. coloration-. 'The same product may also be recoveredby distilling the filtratevwith-steam.

1Q partsjor thefintermediateproduct thus 7' obtained are heated to boiling for about 1 hour withlOO parts of orthodichlorbenzene f I00 and IOpartsOfcrude carbolic' acid. v Inthis manner a vigorous evolution of hydrochloric acid takes place. When the mixture is cooled the new dyestufi crystallizes in the form of small lustrous rhombic crystals. It dissolves in concentrated sulphuric acid giving an orange red colorationand is precipitated as a red fiocculent precipitate by diluting the solution with water. It dyes cotton from a violet vat extremely brilliant bluish red shades.

Example 9 The filtrate obtained as described in Example 1 is heated to boiling for about 1 hour, hydrochloric acid being thus evolved. The dyestufi" which separates in a crystalline form after cooling practically corresponds in its reactions and shade of color with the dyestulf obtained in Example 1. p V r I By working up in the same manner the mother liquors which arise in the production of the dyestuff obtained from 1-orthotoluidoanthraquinone with chlorine in trichlorbenzene as described in Example 1 of the U. S; Patent No. 1,133,081 or in the productionof theproduct prepared by treatment of 1-ani-, lido-2-methylanthraquinone or l-ortho-toluidoanthraquinone with sulphuryl chloride according to Example 1 of the British specification No. 14,360, A. D. 191 1 a brilliant bluish red dyestuff is likewise obtained which is apparently practically identical with the dyestufi hereinbefore described.

What I claim is 1. A process of producing chloroanthraquinoneacridone which comprises treating 1- phenylimino anthraquinone containing a methyl group in ortho position to the imino group, dissolved in a halogen derivative of benzene with a chlorinating agent, separat ing the chlorination product more readily soluble in organic solvents and splittingofi chlorine in the form of hydrogen chloride from the sep-aratedproduct by heating it in an organic solvent in the presence of a phenol.

2. As a new article of manufacture substantially uniform anthraquinonacridone containing about 5 atoms of chlorine, dissolving in concentrated sulphuric acid to give an orange red solution from which it is precipitated as a red flocculent precipitate on dilution with water, dyeing cotton from a violet vat brilliant bluish red shades, which dyestuff yields on boiling; with diethylaniline'an anthraquinoneac'ridone containing about 1 atomsof chlorine, dyeing cotton orange shades, and being converted by the action of chlorine into a product havingthe same tinctorial properties as the initialmaterial.

In testimony whereof'I have hereunto set my hand.

' WALTER BRUCK. 

